Catalytic conversion of hydrocarbon oils



March 19, 1946. R. K. STRATFORD 2,396,758

CATALYTIC CONVERSION OF HYDROCARBON OILS Filed Feb. 18, 1941 CONDENSER FRACTIO VA TIN To WEa Dis nvc OOLER tended to Patented Mar. 19,1946

UNITED STATES PATEN CONVERSION OF immo- CARBON CATALYTIC 1' OFFICE OILS ' mama K. Stratford, Corunna, on'iano; Canada, assignor tov Standard Oil Development Company, a corporation of Delaware Application February 18, 1941, Serial No. 379,415

' 8 Claims. (Cl. 196-52) V This invention relates to the catalytic conversion of .hydrocarbon oils and pertains more par-' ticularly to a process for cracking oils in the presence of a, catalyst powder and to the catalyst therefor.

It has heretofore been proposed to crack oils in the presence of a catalyst into lower boiling hydrocarbons suitable for motor fuels by injecting the catalyst in. the form of-a slurry of catalyst in oil or catalyst in water intoastream of oil vapors to be cracked and subjecting the resulting suspension or mixture-to-catalytie crackin'gin the vapor phase under elevated pressure.

taining. authe water of solution imbibed therein. 1 Such a product, for example, may contain upwards of 90% water and seldom contains less than,80%.-'-

Under-Jess carefully controlled conditions, a

, portion ofthe silicaformed in the hydrosol may For example, a rocess of this general type is described in a. copending application Serial No. 248,164, now U. S. Patent'No.'2,319,'l10; dated May 19, 1943, filed jointly by myself and Roy H. Smith. According to the general type of process there outlined, the oil to be cracked is first vaporized and the oil-catalyst or water-ecatalyst slurry is injected into the oil vapors before passtype of pr'ocessabove outlined.

Other more specific objects and advantages of the invention will be apparent from the detailed description hereinafter in which reference will bemade to the accompanying drawing which is be precipitated immediately inthe form of a fioc'culent gelatinous recipitate which may be also employedin-carrying out the, present in'v'en- .tion. The catalyst employed in carrying out the proc ess heretofore outlined preferably consists of silica hydrosol, hydrog l, latinous precipitate or mix-' tures thereof to which are added other catalytic agents, such as, for'example, alumina, magnesia, boria, zirconia, and the like. These metallic oxides may be added to the. silica hydrosol, hydrogel,

gelatinous precipitate or the like in a hydrous or non-hydrous form, such as in the form of a hydrosol, hydrogel, dry gel, or the commercial grades of oxides which may or may not have adsorptive characteristics. For example, an eifectivej catalyst for carrying out the present process may consist of a plural hydrosol of silica and alumina.

Such a hydrosol maybe formd, for example, by combining an aluminum chloride, aluminum nitrate, aluminum sulfate, or other aluminum salt solutions with asolution of sodium silicate so that the sodium'silicate is partially or completely hydrolyzed by the aluminum salt.. If necessary,

additional acid may be added .to complete the hydrolysis and'form a clear s ution containing both a diagrammatic illustration of an apparatus capable of-carrying the invention into effect.

The present invention is directed to the use of a hydrous oxide or mixture of hydrous oxides, or a mixture consisting of a hydrous oxide and a dry oxide, for making up the slurry injected into the stream of oil vapors to be cracked. The. term "hydrous oxide asherein employed is incan a metallic oxide containing a substantial amount of water imbibed therein,

such as a hydrosol, hydrogel, or gelatinous pre- 'cipit'ate of the various oxides. For example, a hydrosol of silica can be prepared by neutraliz to set into a mixed hydrogel the silica. and )alumina t erein. 'I 'hls product may be injected directly into the-oilstream ore-it may first be allowed to set into a hydrogel which may then be injected intothe oil'stream to becracked l As a furtherexample, a hydrosol of silica may first be formed and an alumina hydrosol then added thereto to form a combined solution of silice and alumina hydrosols. The resulting mixture may be employed directly or may be allowed which is. then injectecl into. the'bil stream.

.As a further alternativegthe ammma or other ,metallic oxide may vbe added in a relatively dry form, such as in-the formof alumina-gel, bauxite,

' -Or the "like, to the silica hydrosol, or it may be ing a sodium silicate solution under carefully I controlled conditions such as isdisclosed in the Patrick Patent No. 1,297,724. B9. properly regulating. the concentration of the acid solution-and sodium silicate solution and byconstant..,.a ltamechanically mixed with the silica hydrogel after forming.

, The important? point i connection with .the

[present invention is the use in the catalytic cracking process of a hydrosol, hydrogel, gelatinous pretion, a clear hydrosol of silica may, be formed which upon standing will set into a hydrogel concipitate, or other hydrous-oxide di'rectlyin the catalytic cracking process without the intermediate orinlieutbereoimaybeincorporated pipe I in a completely vaporised condition. At

this point after complete vaporization, a catalytic agent is introduced, preferably as a slurry in a suitable carrying. liquid, from a vessel 8 by means orapumplandapipe a. Conditionsaread- Justed atthispointaswillbedisclosedbelow, so that the catalytic agent which is in a finelydivided form is immediately dispersed through thevaporizedoilandpassesintoacrackingzone along with the oil vapor. The catalyst dispersion may be added in small amounts and at diflerent points if desired, as at l, b", and 3. The heating zoneisshownonthedrawingasacoil s mounted inasetting i0. lidesiredthecoilmaybesumciently large to provide time for the complete reaction. but, it a longer time or reaction is desired,

' the material from the coil may be passed by means or a line H through a reaction chamber ii. In either case, whether the products pass through the reaction chamber and line Ila or through a by-pass line it, they pass through line Ila and discharge into a iractionating tower it which is provided with iractionating plates I! and a reflux coil l6. Gasoline vapors are withdrawn by vapor pipe l1 and condensed at is and collected at it. If desired, an intermediate cut may be withdrawn from the middle or the tower by a line 20, cooled in the cooler 2i, and may be returned for reuse by hne 22 and pump 23. This material, or a portion 01 it, may be returned to the vessel I throu h line to and thus may serve as a dispersing agent in which the catalyst may be introduced.

The heavier products from the tower it are withdrawn from a pipe 24 and after suitable cooling at 26 are passed through a filter is or other suitable mechanical device for removing the catalyst from the oil. Such oil is preferably sent to storage by pipe 21 but it desired a portion of it may be passed by pipe is and pump is for reuse in the process, either to vessel through line in or to coil I through line 20.

In the above description, two separate coils, one for the vaporization and one for cracking are shown, but if desired both may be mounted the same as in previous setting without departing from the point in question.

In accordance with the present invention, there is introduced into the stream of oil vapors passing through the cracking zone a catalyst slurry formed of a hydrous oxide of silica combined with one Or more metallic oxides, such as alumina, zirconia, magnesia, boria, and the like, as previously described. The amount of such hydrous oxide catalyst introduced into the oil may be in an amount oi. from 0.1 to pounds of catalyst per barrel of oil calculated on the dry basis. In addition to the hydrous oxide catalyst herein described naturally active or activated clays may also be injected through line 30 into the oil stream passing through the cracking zone.

Upon injecting the catalyst slurry into the oil stream, the free water present therein is immediascents I I conversionoithehydrol lorotherproductintoa ateiy vaporlsed by the super-heating vapors, and the catalyst particles are intimately dispersed throughout the oil stream.

Itispreferredtointroducethecataiystinto theoilstream atapointwheretheslurry'iscompletely vaporised without th anyoilvapors. 'I'hiscanbe eved-by adding theeatalystslurryatapointintheheatingsone atwhiehtheinputoiheatisveryhigh, andthe tendency to condense may be onset to a considerable degree by preheating the slurry to as high a temperature as possible without decomposition.

The oil vapor stream may be superheated suiiiciently to provide heat i'or immediately vaporising the water present in the catalyst when the latterisdispersedinthevaporstream.

While it is preferred to introduce the catalyst into the vapors as just described, it is possible to obtain improved results in some cases by introducing the catalyst into the feed prior to or during vaporization.

The oils employed for the present Process should be distillates capable of complete vaporization under the conditions prevailing and the conditions 01' temperature and pressure should be adiusted so as to obtain complete vaporization. The 'oil is preierably preheated to 800 or 850 1". or higher before introduction of the catalyst and the pressure imposed at coil outlet should be at least 200 pounds per square inch, although it is preierable to use considerably higher pressures, say 250 to 1000 or 2000 pounds. I! the oil cannot be vaporized under these conditions, then it should be redistilled so as to produce a lower boiling. out which can be so employed. It is found, however, that the introduction or a considerable amount 01 lighter oil, such as naphtha or hydrocarbon 'gases, assists the vaporization of heavier stocks,

especially when vaporization is carried out in a coil such as provided here. in which the tube size is such as to prevent stratiflcation of the vapor from the liquid phases. In this way it is oiten possible to avoid redistillation and to accomplish cracking of stocks in vapor phase which could not be employed if used in absence of the lighter stock. The lighter oil is also improved somewhat as to volatility and anti-detonation quality. Heavy oils may be distilled or cracked previously by conventional methods in order to obtain a lower boiling stock which can be vaporized under the temperatures and pressures disclosed, but even naphtha stocks may be used if suiiicient light oil is added to insure complete separation of oily constituents.

A coil is preferably provided to serve as the cracking zone so that heat may be added during cracking, that is to say, while the catalyst and the oil vapors are in contact, and the time is provided so that a substantial yield of gasoline is obtained. It is preferable to provide a coil and upilow drum for reaction space and it is found that catalyst stratiflcatiton occurs in the drum and eiiects additional decomposition, so that a greater products. while temperatures in excess oi 1000 F. may be used, it has been found that with an effective catalyst temperature generally need not oitheoii,

condensation of be above 1000 F. with pressure of 200 to 500 pounds and preferably higher with higher temperatures. These conditions in combination with the use of a siliceous catalyst of the class disclosed above introduced where the oil is in the vapor phase are the essential elements.

The oil discharged from the cracking zone may be cooled and clay separated, but it is preferred to separate a light distillate suitable for gasoline and a heavier oil which carries the catalytic ma.- terial. The catalyst may be separated from this oil by mechanical means such as filtration or centrifugation from liquid oil or by vapor by means of cyclone separator but some of the clay appears to accumulate in the reaction drum, if it i employed, and this effects an increase in octane number of the gasoline produced. In the process it is possible to obtain very high yields of gasoline from gas oils with low gas yields and it is not ordinarily necessary to use recirculation methods as are commonly employed in cracking processes.

Having described the preferred embodiment of the invention, it will be understood that it embraces such other variations and modifications as come within the scope thereof What is desired to be protected by Letters Patent is:

1. A method of producing gasoline by cracking hydrocarbon oil which comprises admixing the oil to be cracked with an undried hydrous silica prepared from a metal silicate solution and containing imbibed water and having mixed therewith an active oxide cracking catalyst, passing the mixture of hydrocarbon oil and hydrous silica oxide mixture through a cracking zone, maintaining said cracking zone at a temperature of from 1000 to 1200 F. and under a pressure of at least 200 lbs/sq. in., controlling the temperature and pres.. sure relationship within said zone to keep said 011 in vapor phase therein, withdrawing cracked products from said cracking zone and fractionating said cracked products to segregate a gasoline fraction therefrom.

2. A method of producing gasoline by cracking hydrocarbon oils which comprises vaporizing the oils to be cracked, superheating the oil vapors to a temperature materially above the condensation point thereof, introducing into said superheated oil vapors an' undried hydrous silica prepared from a metal silicate solution and containing imbibed water and having mixed therewith an active oxide cracking catalyst in a substantial amount whereby said silica-oxide mixture is rapidly dried by the superheated vapor without reducing the vapors below the condensation point thereof and solid catalyst particles in finely-divided form are dispersed in the vaporized oil, and passing the resulting mixture through a cracking zone maintained at cracking temperature and under a pressure of at least 200 lbs/sq. in.

3. The method defined in claim 2 wherein the undried hydrous silica oxide mixture consists of a synthetically prepared plural hydrogel of silica and alumina.

4. The method defined in claim 2 wherein the amount of catalyst introduced into said oil vamm is between about 0.1 and 10 pounds of catalyst per barrel of oil, said catalyst being calculated on a dry basis.

5. In a process for preparing motor fuel by passing a hydrocarbon oil feed stock in the vapor phase through a cracking zone under a pressure of at least 200 lbs/sq. in. and temperatures between about 1000 F. and 1200 F. and adding thereto a solid siliceous catalyst and maintaining the vaporous stock and siliceous catalyst in the cracking zone for sufiicient time to effect substantial conversion of the oil to gasoline, the improvement which comprises adding to the siliceous catv alyst-containing oil stream passing to said cracking zone a hydrous oxide Jelly comprising an active cracking catalyst, withdrawing the cracked products from the cracking zone and fractionating said cracked products to segregate a motor fuel fraction therefrom.

6. A method of producing gasoline by cracking hydrocarbon oil which comprises admixing the hydrocarbon oil to be cracked with an undried hydrous silica prepared from a metal silicate solution and having admixed therewith a metal oxideactive as a. cracking catalyst and selected from the group consisting of an oxide in hydrosol form, an oxide in hydrogel form, an oxide in gelatinous precipitate form, a dry oxide gel and a dry oxide, passing the mixtrre of oil and hydrous silicametal oxide mixture through a cracking zone at an elevated temperature and pressure and maintaining the oil in vapor phase, withdrawing cracked products from 'said cracking zone and separating gasoline from the'cracked products.

7. A method according to claim 6 wherein the undried hydrous silica-oxide mixture consists of silica hydrosol and alumina hydrosol.

8. A method according to claim 6 wherein the undried hydrous silica-oxide mixture consists of silica hydrogel and alumina hydrogel.

REGINALD K. B'I'RATFORD. 

